Solvent-soluble metal phthalocyanine compounds and process of making the same



United States t t 12az'snz's Y soLYENnSnLUBLEsMEmn 'LSQMPOUNBSANDTBRQCESS on MAKiNG vTHE is'Viktor WVinnfayn-litaniebergfi 'Y assigner ME. 1.11111 Pont de Nemours .and Company Wilmington; "Deli-,ta ,n'icorporaiorvof'laware n@ Y t ameriten Y invention relates :to a4 :novelseries` fplrthaloeyanine aterifvative's#which` sarelisolnbl'e 'nii organic :solvents such :as acetone; aleohblgfben'zee and pyridine.

tfForeintpleifyfireference;acetone will 'bre usedkhereinafter as typical of said group of yorganic solvente-and 1a substance wiiliibeeens'idered as jselulileinlthi'sstandard, a "finies-emes erein froiftheieirtentef atleast oswby ergibt, :although atSZO*J C., :com :of Ich f'compoundsYv dis- 10% or evenhigher. i, t, u

As is well known, metaliphthalocyanine such as copp'er phthalocyanine, nickeluph'thalocyanine or cobalt phthalot ereignete 'fertibfilityin water and e beton ojrlbe"V the average) to 15.5 or even 16 atoms"p'ermolculehave been known for a long'tirrie. *Brit in their solubility char- 'factcrstics"wyaretrue kto1tl1e'rule;,.'Tlhetyarefinsoluhle in l :water anddh-oiganicfsolvents.

invention-iszibased on thenamazingicdiscovery that r-.met'al phthalocyanines containing fboth uoroslfonyl-z- 'zgroups .tand fnuclear E :halogen fsubs'tituents, @there Lbeingzat j fcyanine,l gbeing'ga-netaleoffthe Igroupconsisting of `copeperfmickelfand cobalt,XSdesignateshalogenselectedirom flheernupecensistinawf uorinehle'tine add-bwminee" i .Y f 4 10 parts (by weight) ofY SF.,t and from 0.5 toy parts t Y Y .is a numeral from 2 to4; and y is a numeral not lessthan fenssen hereinbelew :will dissolveftoin extentasqqigh fas Y' sol wherein y moleculefota rnetalfphthalo- 925,423 @atenten Feb; 16,1960

l1. Aillurther#objectiof'thisinvention yis =to provide prac- V"tical .processesfforsynthesizing compounds of theabove formula. `Various additional objects andv 'achievements irive'rtin-vill'fappear as 'the description proceeds.

nferredijprocess fo'r -rna'nufacturin'g Vsaid commile, 7i theVnunnberofA 'suilfofgroups vin the molecule. 25 l V Altogether, thertritialematerial'niay Lbe denedby the frindla`fr"'1-.p

pr vessaboyeoutlined notlonly. converts theSrOZ n :groups f. into :SQF :L g17o1'1ps,Y but `valso Ntends to introduce *.uorine into ltlre iBznuc1e' i. VAs `a-consequence, y `in the 4:0*` vfinalgiproduote( Formula1 above) will generally be greater than-fz in 'n the ,initial ymaterial ',(Formula ;-II) :provided z Y .fis, .lnotx near.its upper :lim'itfof (16e-n). y

.-Furftherinore, -where :the initial material has no halogen1-ahah or only ia loiw eontentthereof, the product vof the:autoclaving-treatmentmaybe subjected to halogena- 'tion in known manner to introduce additional halogen ipaftomsgfinto' the f nuclei, which halogen atoms .may be Jeb-lening bromineior-rnore luorine. t

Finally, I may treat .the initial .materia1-of;Formula II above with agents adapted onlyrto replace Z in the group SOZZ by uorine, Le., withoutachieving simultaneous norination in thewring; s If Hthe.initialtn'iaterial has no 'nclearlhalogenj(ie, z=0 .,in .Formula'II the product j oflthfis tneatnentrnay befisolated and thenk treated with 55,'iagehts);adaptedgto .introduce'fhalogen (.F, C1 Aor Br) .into thefrBZ-rings. Afsimple illustration. .of :such alternative qproces'slissthe treatmentof copper phthalocyanine tetraa `StiltonylYehloride in an 1autoclave .with a solution of'potaside,''inihydrogen:iluoridey f `may ,represent various .combinationsgof ,Claudi F, IBrY and preferredqorocess `:above set..for'th 'may .varytfromll to oni-'prises' Ehea'tnga metal `phtlralocyanine poly-tl g'kanaflkylfester o'f'l'to 4 Csatoms in the 'alkylVv tygaiffonanriae; erafnuelearahnegen :dertvativeefw 4actin'g-iu'ponthe'latterwith afdesirable vhalogeriating agent, .I ,f-suohfas Vclglofrin'ev, bromine, ;sulfurmcnochloride:or sulfur ll-be 4clear from the VAafvoregomgv availblernetliods; y ntbesis that Xycinthe'iormulapf tthe productis' i `notllmitecl Ito representingra single halogen;instead,' fit' upon this invention.

of HF per part of initial polysulfo metal phthalocyanine. The preferred duration of the heating is best determined by experiment and observation of the results. One hour will give a quantity of acetone-soluble product in some cases, but a longer period generally increases the yield. Two to six hour may be taken as an optimum period for most cases.

The theory of the reaction is not altogether clear to me, and should not be taken in any sense as a limitation But for the sake of making the understanding thereof clearer, I oier the following as a probable hypothesis for the course of the reaction.

The sulfur tetrafluoride acts on therSOgZ groups, converting them into SO2F groups, and in combination g with HF it acts further on the benzene nuclei to replace some of the H-atoms (if such are still available) by fluorine.

An incidental, equally unexpected, but most valuable property of my novel compounds is that they possess i This valuable collateral property makes my novel corn-l v pounds useful in many fields where hitherto known phthalocyanine compounds have not been applicable. For instance, inasmuch as the novel compounds of this invention are not attacked byrperoxides, they may be;

incorporated as colorants into monomers which are to be polymerized by the aid of dibenzoyl peroxide or similar catalysts Vinto plastics. Y

My novel compounds may also be utilized where their green, and usually light-fast dyeings on most of them. They may also be incorporated into inks and lacquers, from which printings can be made exhibiting the exceptional light-fastness and pleasing brilliance of the phthalocyanine colors in general. On the other hand, they may also be used as pigments, like hitherto known phthalocyanines, but with the added advantage that the resultsolubility in organic solvents shows up to-advantage.,.I Y For instance, they may be applied to textile fibers from -organic solvent solution, to produce brilliant blue to ing prints or coatings possess high stability to fading Y by oxidiation.

Without limiting this invention, the following examples are given to illustrate my preferred mode of operation. Parts mentioned are by weight.

Example 1 Ten parts of the sodium salt of sulfonated copper phthalocyanine (obtained by direct sulfonation of copper phthalocyanine and containing an average of 2.4 sulfo groups per molecule), 90 parts of anhydrous hydrogen fluoride, and 30 parts of sulfur tetraliuoride were charged into a stainless steel bomb which had been cooled in a Dry Ice-acetone mixture and had been swept with nitrogen. The bomb was closed and put into an oil bath where it vcould be agitated. The temperature of the oil bath was raised to 150 C. over a period of about four hours and the bomb was agitated at'an oil bath temperature of 150 to 155 C. for six hours. After cooling the bomb to room temperature it `was cooled further in iced water and the remaining pressurefmainly due to an excess of sulfur tetratluoride, was released. The reaction mass was then poured onto about 200 parts of ice, filtered, washed nearly acid free, slurried in 200 parts of dilute aqueous ammonia to neutralize all hydrogen lluoride, filtered and washed again with water, and dried at 80 to 90 C. The deep blue solid thus ob solution on ice.

4 A tained was extracted with acetone. Upon evaporation of the acetone, 4.9 parts of a uorinated copper phthalocyanine was obtained.

Analyses of the new blue dye showed a NzF ratio of about 1:1. Inasmuch as there are 8 N-atoms per molecule, and inasmuch as the initial material contained, on the average, only about 2.4 sulfo groups per molecule, and since. it appears logical that each S03Na group is converted in the above reaction to SO2F, it follows from the above analysis that considerable nuclear liuorination has taken place, resulting in fact in some5 to 6-nuc1ear F-atorns per molecule.

The acetone and benzene solutions tof' the reaction product were blue; sulfuric acid solutions were green. The product showed also marked.` solubility in many other organic solvents. It was also highly resistant to oxidation with a hot dilute sulfuric acid-ceric sulfate solu-V tion, whereas the starting material was readily oxidized-in this solution at room temperature. rThe new product was also very resistant to oxidation with boiling nitric acid. Upon oxidation with.fuming nitric acid, a

high yield of a sulfonyl luoride of phthalimide was obtained. e

The fluorinated copper phthalocyanine of this example did not lose its solubility in organic solvents by heating it in sulfuric acid to 130 C. and drowning the Neither did it become wateror ammonia-soluble by that treatment.

Example Z Twenty parts of the potassiumY salt of a copper phthalo- Y cyanine tetra(4)su lfonic acid (made from v4sulfophthalic ,acid), V60 parts of anhydrous hydrogen iiuoride, and 30 parts of'sulfur tetrauoride were heated in a nickel bomb ,to 150 C. for 6 hours.

Afterl isolation of the reaction product and extraction with v acetone as described in Example 1, 7.5 parts of acetone-soluble blue product were obtained.A Analyses of the new blue dye gave a ,N:F ratio of 1:1, which indicates that the product is copper tetralluoro-phthalocyanine tetrasulfonyl fluoride. 'lheV tetrasulfo starting material was readily oxidized by aqueous, acidic, ceric sulfate at room temperature, but the fluorinated reaction product was oxidized in the same medium only upon heating. Upon oxidation of the new soluble` dye with fuming nitric acid at the boil, Va sulfonyl liuoride of phthalimide was obtained.

The soluble dye of this example was also stable upon heating to C. in 100% sulfuric acid, and remained waterand alkali-insoluble, and organic-solvent-soluble after that treatment.

Example 3 Two parts of a copper phthalocyanine sulfonyl chloride containing an average of three sulfonyl chloride groups for molecule, and made by reacting copper phthalocyanine with chlorosulfonic acid, 20 parts of anhydrous hydrogen iuoride, and 7 parts of sulfur tetraliuoride were heated at C. for six hours, and the reaction product was isolated, as described in Example 1. 1.4 parts of acetone-solublev uorinated reaction'products were obtained, whose analyses showed a NzF ratio. of 1:1. It also contained chlorine. The acetone-soluble product was insoluble in hot dilute aqueous ammonia. It was soluble in 100%v sulfuric acid and was recovered from it (by ',drow'ningin `water and filtration) in its original, water insoluble, organicrslovent-soluble form.

Example 4 Y Two parts of the potassium salt of nickel phthalocyanine disulfonic acid (prepared by sulfonating nickel phthalocyanine in 20 parts of 10% oleum, drowning in dilute KCl solution, filtering and washing with 15% KCl solution), 20 parts of anhydrous'hydrogen liuoride, and 5 parts o f sulfur tetraliuoride were heatedrat 150 C. under autogenous pressure for Vsix hours. Upon dilution and extraction with acetone in the manner hereinabove lretiren-or'genie solvents, with-a-blie-eolor -was obtaii'ied-il su onyl chlorides, fand-"icon '(KF.2H2O) and 80 parts of anhydrous hydrogen uoride lvere heated in a closed nickel vessel.at150 C. vfor'4 ours.

vk1o The reaction mass was then cooled and poured on ice. YThe blue precipitate was filtered, washed acid A amples, technical hydrogenvuoride- VVhasbeen" used by me Thelaftsssastairsuasss @moisture Thus, an-

Yhydrous'HFis'i"notf'an `absolute''requirement wf orthis reaction, but is a desirable gnhfrom the practical viewpoint,

rrosiv :maniement In the synthesis employing metal-phthalocyanine sulfonicacids or salts thereof, the reaction mass should contain at least 0.5 part byweight of HF and at least 1.0

part of SP4 per part ofthe initial metal phthalocyanine compound. But I.know of no theoretical upper limit,

except the obvious consideration that the larger the exanhydrous potassium lluoride was used instead of the di'- hydrate,

.l Example 6 ride prepared as described in Example and 75 partsfof. anhydrous hydrogen uoride were cooled in'a nickel ves- Asel in a DryIce-aceton'e bath, and 5 parts `ofchloriue were added. The vessel was closed andthe charge was then heated over a period of two `hours to 100 C. and

agitated at 100 C. for two hours. The reaction massVv '25 VFive parts of copper phthalocyanine polysulfonyl fluo- Y cess of either gas employed, the larger the expense of subsequent'recovery. Consequently, upper limits of 50 parts of HF by weight and l0 parts of SF4 are recommended as a matter of economy.

I claim as my invention:

1. A compound of the formula Y SOfF) n MPc wherein MPcdesignates the molecule of avmetal phthalocyanine, M being Yarrnetal of the lgroup consisting of copper, nickel and cobalt, X designates halogen Yselected fromv the* group consisting ofy iluorine,V chlorine andl was then poured on ice, and 4 parts of a dark green solid were isolated and then extracted with acetone. vUpon evaportaion of solvent from the green solution, a green j solid containing chlorine was obtained. This product was readily soluble in acetone with a green color,

while the'unchlorinated'startingmaterial was onlyV slightly f soluble vin acetone with a blue color. Y

Example 7 Five parts of a mixture of copper phthalocyanine polysulfonyl uoride as obtained in Example 5 were added to 25 parts of sulfur dichloride which'had been cooled in a stainless steel bomb in a Dry Ice-acetone mixture. 90 parts of hydrogen iluoride were then added, and the charge was heated at 150 C. for six hours, under autogenous pressure. The reaction mass was cooled, poured on ice and the precipitate was isolated in the usual manner. This precipitate amounted to 4 parts and was contaminated with elemental sulfur.v Upon extraction with acetone Iand evaporation of solvent from the green solution, a green solid was obtained which analyzed ashaving a ratio of N:CI:F=8:12.2:5.'5.

Example kv8 Three parts of bromine were Put into a vckel vessel vand cooled in a Dry Ice-acetone mixture. 5 lparts of a mixture of copper'phthfalocyanine polysulfonyl uorides from Example 5 were added, followed by 60 parts'of anhydrous solvent, a green product readily soluble in acetone with a green color was obtained.

It will be understood that the details of procedure may be varied widely within the' skill of those engaged in this art. lf nickel chloride or cobalt chloride lis used in lieu of the copper salt in the synthesis of the phthalocyanne Copper phthalocyanine.

pared to copper phlthalocyaninc.

bromine, vn is .a numeral from 2 to"4, and y is anumeral 7 'not less thanl, said Vcompound being characterized by greater solubility in acetone and by increased resistance to oxidation in acidic aqueous ceric sulfate solution comparedto the correspondingunsubstituted phthalocyanine VVcompound of form MPc. 2. Copper polyhalogeno-phthalocyanine' polysulfonyl iiuoride, vwherein the halogen is of atomic number not exceeding 35, said compound being characterized by greater solubility in acetone and by increased resistance to oxidation in acidic aqueous ceric sulfate solution com- 3. Copper polychloro-phthalocyanine fluoride, the number of chlorine atoms being not less than 4 and not more than 12 per molecule, said compound being-characterized by greater solubility in acetone and by increased resi-stance to oxidation'in acidic aqueous ceric sulfate solution compared to copper phthalocyanine.

4. Copper tetrauoro-phthalocyanine tetrasulfonyl iluoride,esaidrcompound being characterized by greater solubility in acetone and by increased resistance to oxidation in acidic aqueous ceric sulfate solution compared to 5. EThe process of producing an acetone-soluble metal phthalocyanine, which comprises heating together :under autogenous pressure a metal phthalocyanine compound of the group consisting of metal phthalocyanine polysulfonic acids, their alkali-metal salts, metal phthalocyanine polysulfonyl chlorides,v4 metal phthalocyanine polysulfonarnidea metal phthalocyanine polysulfonic "ac id lesters and the nuclear halogen derivatives of any of these, and a mixture of sulfur tetrauoride and hydrogen v 'A fluoride, whereby to obtainanuclearly uorinated 1I1 etal phthalocyaninespolysulfonyl fluoride.

v ing and chlorinating agents, kwhereby to introduce additional halogen into vthe Bz-nuclei of the compound.

compound, the Vresultingmetal polysulfophthalocyanine, when carried through the procedures of the above examples, will lead to acetone-soluble derivatives of nickely and cobalt-phthalocyanine, respectively.

Y7.7A'process as in lclaim l5, Vwherein'othe reaction is;v

achieved-by heating a mixture of the reactants, under autogenous pressure at a temperature between and IC.v

8. TheV process of producing an acetone-soluble copper phthalocyanine, which comprises heating together under' Y autogenous pressure copper'phthalocyanine-tetrasulfonico issssuchaahydfogen slacaneisiag Weisse, highly tetraisulfonyl 6, process asinY claim'- 5, including the further step; l lof reactingupon the compound thus produced with ai, halogenating agent of the group consisting of brominat- References Cited the le of this patent y 5 1 v UNITED STATES` PATENTS I 2,225,441 Braun e: a1.".".`..' Deel` V17, 1940 

1. A COMPOUND OF THE FORMULA 